This study investigates how users’ cognitive and affective characteristics influence their navigational and search behaviors on the Web among the experienced Web users. Eighty undergraduate students participated in the study. Two standardized tests and a questionnaire were used to collect information on the participants’ cognitive style, problem-solving ability/style, and demographics. Factor analysis was performed on the scores from the two standardized tests (Group Embedded Figures Test and Problem Solving Inventory), and extracted two user factors (Focus Control and Emotion Control). Focus control factor seemed to influence users’ navigational behaviors, such as the use of links and back buttons, whereas Emotion control factor affected search behaviors including keyword searching, and also search performance measured by precision and recall. The study suggests that different user characteristics influence different aspects of user behaviors: Some are more closely related to the execution level and others to planning level of a search. Based on the findings, suggestions are made for user training programs and also for the future studies.